JP2019529676A - XRF identifiable transparent polymer - Google Patents

Abstract

The present invention provides blends and masterbatches of polymeric materials and XRF identifiable markers to produce transparent elements comprising polymers and at least one XRF identifiable marker for various industrial applications.

Description

  The present invention relates generally to transparent polymers containing fluorescent X-ray identifiable markers and methods for marking and authenticating transparent products.

  Transparent polymers are widely used in products in various fields and industries such as buildings and buildings, healthcare, packaging, household goods, electronics and appliances, and in the automotive and aircraft industries.

  Transparent polymer products such as pipes, wire insulation, weatherstrips, fences, deck rails, plastic films and sheets are produced by several methods such as extrusion, molding and forming methods. Extrusion involves forming an unprocessed plastic melt into a continuous profile. The raw feedstock material for the extrusion process is typically a solid plastic material in the form of a resin, which is fed from the top mounted hopper to the extruder barrel.

  Defects or deviations in the polymer product (eg, plastic product) from the manufacturing process specifications can result from improper installation or operation of the extruder, insufficient mixing of ingredients or addition of materials, overheating, and the like. The resulting defective product may exhibit product thickness or wall thickness fluctuations, bubbles and indentations, contamination by foreign objects, inhomogeneities, and even non-dispersed additive particles. Some of these defects are difficult to detect and identify during continuous manufacturing.

  In addition, it is difficult to detect product degradation during use (eg, detection of defects) due to exposure to various conditions such as temperature, exposure to sunlight, and exposure to oxidized materials after production of the polymer product. .

  X-ray fluorescence (XRF) has been used in the past to identify products based on XRF markings present on the products. In XRF, characteristic “secondary” (or fluorescent) x-ray emissions from materials excited by primary or gamma radiation are detected. The term fluorescence absorbs radiation of a particular energy and results in a re-emission of radiation of a different energy (typically lower). The XRF phenomenon emits electrons from atoms in the inner orbital when the material is exposed to short wavelength x-rays or gamma rays, so that electrons in higher orbitals “fall” into lower / inner orbitals, And based on the fact that the process emits photons with energy equal to the energy difference between the two relevant orbitals.

  Since different chemical elements have electron trajectories / shells of different characteristic energies, the spectral profile of the XRF response from the object / material indicates the chemical elements and possibly the amount of each element contained in the material / object.

  US Pat. No. 6,332,940 [1] is directed to a process for producing a BOPP film containing 10-50% w / w calcium carbonate.

  US Pat. No. 8,427,810 [2] is directed to the measurement of residues in BOPP film by XRF analysis.

  U.S. Pat. No. 8,590,800 [3] is specifically directed to the introduction of markers into plastic products.

  None of these publications address the challenge of marking and authenticating transparent polymer products without departing from the initial optical and mechanical properties of the product.

  Accordingly, there is a need for a technique that has the ability to monitor deviations in the continuous production of transparent polymer products and attempt to maintain the initial properties of such products.

US Pat. No. 6,332,940 U.S. Pat. No. 8,427,810 US Patent No. 8,590,800

  The invention disclosed herein utilizes a fluorescent X-ray (herein “XRF”) marker for marking and authenticating transparent polymer products, specifically thermoplastic products. With respect to the method, this provides an indication of whether the product is defective or whether the product has deviated from a predetermined continuous manufacturing process.

  The technology disclosed herein is not only to detect and identify the deviation of the transparent polymer product during the continuous manufacturing process, but is also subjected to various conditions such as temperature, sunlight, oxidizing material, irradiation, etc. after manufacturing. It is also limited to detecting and identifying deviations in these products due to.

  The marking method involves the application or addition of XRF detectable markers to transparent polymer products and thereby authenticating them, i.e. products from predefined features specified in the product manufacturing process specifications during continuous manufacturing. Whether one or more of the changes in characteristics of the product (ie, product thickness, structure, bubbles and indentations, contamination by foreign matter during manufacture, heterogeneity, and non-dispersed additive particles, etc.) Is based on detecting.

  As such, the combination of transparent polymer element and XRF marker is, for example, but not limited to, the building and construction industry, healthcare, packaging, household goods, electronics and appliances, food packaging Desirable in certain applications such as industry, medical applications, where the use of XRF markers for authentication and identification is particularly desirable. However, when XRF markers are combined in an element, the element becomes inferior in properties, i.e. the optical properties (e.g., transparency, gloss, haze) and integrity of the element compared to an element without a mark. Getting worse.

  Accordingly, it is an object of the invention disclosed herein to be a transparent polymer product with an XRF identifiable marker that has substantially the same physical properties as a raw product (ie, does not include an XRF identifiable marker). It is to provide what maintains (transparency, gloss, strength, thickness, etc.).

  In one of its aspects, a transparent element comprising a polymer and at least one XRF identifiable marker is provided, said element comprising 50-200 ppm of at least one XRF identifiable marker, said element comprising said Having at least one optical property that is substantially identical to at least one optical property of a polymer that does not include at least one XRF-identifiable marker.

  An element according to the invention disclosed herein refers to a transparent polymer having a defined shape and / or structure, and is at least one XRF specific that is incorporated into the bulk of the element (the material volume itself) or a predetermined region of the surface. Includes possible markers. For example, the element can be in a form selected from articles, films, sheets, pellets, plastic parts, substantial two-dimensional structures, three-dimensional structures, and the like.

  The element can be provided as an independent element or can include two or more transparent materials attached to each other to form, for example, a laminate, sandwich structure, multilayer structure, laminated structure, and the like.

  As used herein, the term “polymer” should be understood to have the general meaning known to those of skill in the art. Without limitation, the polymer utilized in accordance with the present invention can be a plastic material. In some embodiments, the polymer is a thermoplastic polymer, i.e., exhibits a property that a solid or essentially solid material turns into a thermoflowable material upon heating and reversibly solidifies upon sufficient cooling. The term also means having a temperature or temperature range at which the material becomes a heat flowable material.

  In some embodiments, the polymer is a polyolefin (eg, high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP)); polyethylene terephthalate (PET); polystyrene (PS); polyvinyl chloride (PVC). ); Polyurethane (PU); polyamide (PA); polyacrylonitrile; polyimide; polyvinyl alcohol and biaxially oriented polymer.

  In such embodiments, the polyolefin is selected from polypropylene and polyethylene.

  In some embodiments, the polymer is a biaxially oriented polymer. In some embodiments, the biaxially oriented polymer is biaxially oriented polypropylene (herein, “BOPP”).

  Biaxially oriented polymer (herein “BOP”) generally refers to a polymer that can be stretched to a predetermined degree without breaking in both the machine direction (longitudinal) and the transverse direction (transverse). Resulting in a polymer having high strength, density, flatness and transparency. The length of the sample increases while stretching in the longitudinal direction, and subsequently the width of the sample increases when the sample is stretched in the transverse direction.

  Biaxially oriented polymers such as biaxially oriented polypropylene transparent elements (eg, BOPP film) are used as packaging films in a variety of applications. These are particularly advantageous because they have various properties such as high transparency, gloss, water and oxygen barriers, integrity, and hardness.

  The combination of BOP and fluorescent X-ray (herein “XRF”) markers is particularly desirable in certain applications, such as in the industry where biaxially oriented polymer films are generally utilized, for foods, food packaging, pharmaceuticals Wrapping films for marking commodities typically used by humans or animals, such as cosmetics, veterinary products, alcoholic products and the like. However, the techniques described herein are not limited to this particular application, but may be utilized for a variety of other applications such as electrical applications, printing, flower packing, pressure sensitive tapes and laminations. it can.

  In another aspect, a transparent element (eg, a film) comprising a biaxially oriented polymer (BOP) and at least one XRF-identifiable marker is provided, the element comprising 50-300 ppm of at least one XRF-identifiable marker. And the element has at least one optical property substantially identical to at least one optical property of the biaxially oriented polymer that does not include at least one XRF-identifiable marker.

  An XRF identifiable marker according to the present invention comprises at least one compound or element identifiable by an XRF signature, ie can be identified by XRF analysis (eg, by an XRF analyzer) and A material that can be incorporated into a polymer element without substantially affecting the physical properties (i.e., optical and mechanical properties) of the same polymer element that it does not contain. XRF analysis, ie analysis of response X-ray signals, can be performed by a suitable spectrometer such as an XRF analyzer that can operate in an uncontrolled environment without vacuum conditions (eg, benchtop, mobile or handheld) Energy dispersive XRF analyzer, which can be a device).

  The markers utilized in accordance with the present invention can be dispersed in the polymers disclosed herein or in formulations for providing elements in accordance with the disclosed invention, further details are provided below.

  The XRF identifiable marker may be in the form of a salt, inorganic or organic material, may be in the form of a metal ion or metal ligand, or may be in the form of a material containing a metal atom, Or any combination thereof may be used.

  In some embodiments, the XRF identifiable marker comprises a material that includes at least one metal salt or at least one metal atom. Some examples of salts included herein include potassium hydroxide, potassium iodide, potassium bromide, aluminum hydroxide calcium phosphite, calcium hydroxide hydrate, calcium butyrate, calcium chloride, sulfoalumine. A copolymer of calcium acid, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, monoethyl ester, calcium salt, titanium dioxide, n-octyltrichlorosilane and aminotris (methylenephosphonic acid) pentasodium salt Coated titanium dioxide, titanium nitride, titanium dioxide nanoparticles reacted with octyltriethoxysilane, manganese pyrophosphate, manganese chloride, manganese hypophosphite, manganese oxide, manganese hydroxide, brass, bronze, copper, stainless steel, tin As well as copper and tin And iron alloys, iron oxide, iron phosphide, cobalt oxide, copper iodide, copper bromide, copper hydroxide phosphate, zinc sulfide, zinc hydroxide poly (zinc glycerolate) hexadecyltrimethylammonium bromide, bromide Examples include, but are not limited to, sodium, ammonium bromide, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine-1,2-dibromoethane copolymer.

  In some embodiments, the XRF identifiable marker comprises a material that includes at least one metal salt or at least one metal atom.

  In some embodiments, the at least one metal salt is selected from zinc oxide, manganese stearate, manganese chloride, zinc diricinoleate, potassium bromide, sodium bromide, titanium oxide, titanium nitride, ammonium bromide and calcium butyrate. Is done.

  In some embodiments, the at least one metal salt is selected from zinc oxide, manganese stearate, manganese chloride, potassium bromide, sodium bromide, titanium oxide, titanium nitride, ammonium bromide, and calcium butyrate.

  In some embodiments, the at least one metal salt is selected from titanium oxide and zinc oxide.

  In some embodiments, the at least one metal salt is or includes titanium oxide.

  In some embodiments, the XRF identifiable marker is a material having an XRF signature and can be selected in a form that includes one or more elements that are identifiable by XRF. In some embodiments, the XRF identifiable marker is or includes at least one element of the periodic table of elements and is characteristic of the element in response to X-ray or gamma ray (primary radiation) radiation. Emits an X-ray signal (secondary radiation) having a spectral feature (ie a peak at a specific energy / wavelength) (X-ray response signal as an XRF signature). An element having such a response signal is considered XRF sensitive.

  The XRF signature may depend on the marking (s) (material composition, concentration, etc.) as well as the surface / structure of the particular product on which the marking is embedded.

  In some other embodiments, the XRF identifiable marker is safe for human or animal use.

  In some embodiments, an XRF identifiable marker is an element or material that includes one or more elements, and the element has an electronic transition between atomic energy levels that produces an identifiable X-ray signal.

  In some embodiments, the XRF identifiable marker comprises at least one metal atom. In some embodiments, the XRF identifiable marker is Na, Si, P, S, Cl, K, Ca, Br, Ti, Fe, V, Cr, Mn, Co, Ni, Ga, As, Fe, Cu. , Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Ag, Cd, In, Sn, Sb, Te, I, Cs, Ba, La and Ce. Contains or contains at least one atom. In other embodiments, the XRF identifiable markers are Na, Si, P, S, Cl, K, Ca, Br, Ti, Fe, V, Cr, Mn, Co, Ni, Ga, As, Fe, Cu, One or more selected from Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Ag, Cd, In, Sn, Sb, Te, I, Cs, Ba, La and Ce It is a material containing the atoms.

  In some embodiments, the XRF identifiable marker is or includes at least one atom selected from Co, Cu, Na, K, Zn, Ca, Mn, and Ti.

  In some embodiments, the XRF-identifiable marker is or includes at least one atom selected from Na, K, Zn, Ca, Mn, and Ti.

  The amount of XRF identifiable marker is essentially homogeneously distributed throughout the element. XRF identifiable markers may also be distributed in specific areas of the element.

In some embodiments, the XRF identifiable marker is selected according to the materials listed in Table 1 below.

  Deviations in the appearance of the elements of the present invention and raw elements that do not add markers are determined, and according to the disclosed invention, when scored in a score test having a range of “0” to “5”, “0” "Means essentially no deviation in the optical properties of the element (appearance in terms of transparency, haze and gloss) or a small deviation that cannot be detected with the naked eye," 1 "means optical Means small deviations in properties (scores “0” and “1” are also referred to herein as “substantially identical” as further details are shown below) and confirmed with the naked eye Yes, but at an acceptable level, and “5” means a deviation in optical properties that can be clearly detected at a level that is unacceptable by the naked eye (eg, opacity as defined below).

  One of the optical properties said to be unaffected by the addition of marking material to the element of the present invention is the transparency of the element. In general, “transparency” refers to a physical property that allows light to pass through a material without scattering. The transparency of the object can be determined by measuring the total transmittance. The total transmittance of incident light on the object is the ratio of transmitted light to incident light. A transparent element according to the present invention is an element that has a total light transmission of at least 80% (for example as measured according to ASTM-D1003-77). An opaque element is defined as an element having a maximum light transmittance of 70% in accordance with the disclosed invention.

  Alternatively, transparency can also be determined by measuring the light transmission through the material with respect to the total percentage of light passing through the material per given width in accordance with the disclosed invention.

  Additionally or alternatively, the optical property referred to herein is the haze of the element, which is the percentage of transmitted light that is scattered when passing through the element at an angle greater than 30 °.

  Additionally or alternatively, the optical property referred to herein is the gloss of the element, which is the ability of the element to reflect light with specular reflection, such as a mirror, and the angle of the reflected light is , Equal to the angle of incident light.

  As will be appreciated, the elements disclosed herein have surprisingly good optical properties that are substantially identical to those of elements that do not include a marker. According to the disclosed invention, the term “substantially identical optical properties” refers to a deviation of at least 90% in the optical properties of the element comprising the marker as compared to the element without the mark. For example, if the transparency of an unmarked element and a marked element is 95% and 92% (measured as total transmittance), respectively, the two elements are said to have the same transparency of about 97% The

  In some embodiments, the element has at least one optical property (eg, transparency, haze, and gloss) that is at least 90% identical to at least one optical property of the polymer that does not include the at least one XRF-identifiable marker. (Also indicated herein as a score “0”).

  In some embodiments, the element has at least one optical property and at least 95%, sometimes at least 92%, at least 93%, at least 94%, at least 96% of the polymer that does not include the at least one XRF-identifiable marker. Having at least one optical property (eg, transparency, haze and gloss) that is at least 97% or at least 98% identical.

  As referred to herein, the term “substantially identical” should not be limited to identity in the optical properties of the elements, but is derived from the density, thickness, strength, hardness, Any properties including surface energy, moisture barrier (water vapor and oxygen permeability), etc. should also be included.

  It is generally known in the art that low levels of impurities such as aluminum, silicon, titanium or boron residues can affect the optical properties of elements such as properties including transparency, haze and opacity. It has been. In some embodiments, the films disclosed herein have a haze of 10 or less or at least 90% transparency (when both are measured, for example, according to ASTM D1003-92).

  Table 2 below shows some XRF identifiable markers of the disclosed invention that are capable of maintaining physical properties in the polymer element similar to those of the unmarked polymer element. That is, XRF identifiable markers can be added to the disclosed elements of the invention without adversely affecting the appearance of the element (or with very little effect).

  By utilizing the markers described herein at a suitable concentration, a transparent element is obtained because the marker concentration can affect the optical properties of the element.

  The concentration or amount of XRF identifiable marker in the element according to the invention is 50-300 ppm.

  In some embodiments, the element is 50-300 ppm, 50-290 ppm, 50-280 ppm, 50-270 ppm, 50-260 ppm, 50-250 ppm, 50-240 ppm, 50-230 ppm, 50-220 ppm, 50-210 ppm or Contains at least one XRF identifiable marker at a concentration of 50-200 ppm.

  In some embodiments, the element is 50-190 ppm, 50-180 ppm, 50-170 ppm, 50-160 ppm, 50-150 ppm, 60-200 ppm, 60-190 ppm, 60-180 ppm, 60-170 ppm, 60-160 ppm, At least one XRF identifiable marker is included at concentrations of 60-150 ppm, 100-200 ppm, 100-170 ppm, 100-160 ppm.

  In some embodiments, the element comprises 50-200 ppm of at least one XRF identifiable marker.

As noted above, if the transparent polymer element includes an XRF identifiable marker in an amount that is not within the ranges disclosed herein, the resulting element's appearance may deviate as compared to an unmarked element. For example, as shown in Table 2 below, inserting certain markers that are higher than the minimum concentration shown in Table 2 (or in some cases, lower than the range specified herein) Provides a noticeable effect such as coloration, haze or opacity on the element. Such an effect can be used to generate the desired effect. For example, colored stripes on plastic elements such as colored tearable stripes on tobacco packs are used for packaging. A number of markings can be introduced into a single product using the appreciable impact. For example, in multilayer films and in addition to transparent delocalized XRF marks, it can also be used for visible marking of areas marked locally with XRF marking.

  The ratio between the XRF identifiable marker in the element and the polymer is sufficient to produce 50-300 ppm of XRF identifiable marker in the polymer.

  The element may further comprise additives that provide the desired visual effect or physical properties.

  In some embodiments, the element comprises an antiblocking agent, an organic pigment, an inorganic pigment, a fluidity enhancing additive, a mechanical property enhancing additive, a non-tacky adhesive, an adhesion promoter, an adhesion inhibitor, a lubricant addition. Agent, anti-wear additive, anti-static additive, marking additive, conductive additive, thermal conductive additive, magnetic improvement additive, insulating material additive, foaming agent, accelerator, catalyst, antioxidant, UV stable Further included are additives selected from agents, flame retardants, pigments, stabilizers, wetting agents, empowers, diluents, wetting modifiers, dispersants, surfactants, diluents, thickening additives and fillers.

  As noted above, references to “substantially identical” should not be limited to a particular property, such as any of the optical properties, but are derived from unmarked elements, density, thickness, strength All properties should be included, including hardness, surface energy, moisture barrier (water vapor and oxygen permeability), and the like. Accordingly, yet another object of the present invention is to provide an element comprising an XRF marker having a desired density and thickness. The addition of the marker typically affects the density and thickness of the transparent polymer. The inventors have found that the elements disclosed herein maintain substantially the same density as the density of the unmarked elements.

  With respect to other “substantially identical” properties according to the disclosed invention, the thickness of the marked element is substantially the same as the thickness of the non-marked element of the same polymer. Although the density of the element may vary as a result of the addition of salt to the element, the invention disclosed herein provides an element having a thickness in the range of 10-100 μm. In some embodiments, the element thickness is 10-90 μm, 10-80 μm, 10-70 μm, 10-60 μm, 10-50 μm, 10-40 μm, 10-30 μm, 10-25 μm, 20-90 μm, 20-20 μm. 80 μm, 20-70 μm, 20-60 μm, 20-50 μm, 20-40 μm, 20-30 μm, 25-90 μm, 25-80 μm, 25-70 μm, 25-70, 25-60 μm, 25-50 μm, 25-40 μm, It is in the range of 25-35 μm, 30-60 μm, 30-50 μm, or 30-40 μm.

  In some embodiments, the element (eg, film) comprises BOP and 50-300 ppm of at least one XRF-identifiable marker and the thickness is between 10-100 μm. In such an embodiment, the thickness is 10-90 μm, 10-80 μm, 10-70 μm, 10-60 μm, 10-50 μm, 10-40 μm, 10-30 μm, 10-25 μm, 20-90 μm, 20-80 μm. 20-70 μm, 20-60 μm, 20-50 μm, 20-40 μm, 20-30 μm, 25-90 μm, 25-80 μm, 25-70 μm, 25-70 μm, 25-60 μm, 25-50 μm, 25-40 μm, 25 It is between ˜35 μm, 30-60 μm, 30-50 μm or 30-40 μm.

  A further object of the present invention is to provide elements having improved mechanical properties such as, but not limited to, tensile strength and modulus, flexural strength and modulus, hardness, toughness, elongation.

  In another aspect thereof, a laminate is provided that includes at least one layer that includes the elements disclosed herein. This element can be combined with at least one additional identical layer or with at least one different layer. This element may be a first base layer bonded to another layer, or an intermediate layer disposed between other layers of the laminate. The combined layers provide a laminate that does not substantially degrade the physical properties of the single layer of the element. Thus, in some embodiments, the laminate further includes at least one transparent layer. In such embodiments, the at least one transparent layer is or includes at least one of a UV blocking layer, an adhesive layer, an oxygen barrier layer.

  Sometimes, in order to bond an additional layer to an element of the present invention, typically by techniques known in the art (eg, by corona), modification of the surface energy of the element may result in adhesion of any one of the layers. May be needed to improve

  The elements disclosed herein can be utilized in applications generally known in the field of transparent polymer elements and are typically human or food, food packaging, pharmaceuticals, cosmetics, veterinary products, etc. Includes packaging film for marking commodities used by animals. However, the techniques described herein are not only limited to this particular application, but also other applications such as electrical applications, printing, flower packing, pressure sensitive tape and lamination, pharmaceutical disposable packaging, medical devices, etc. It can be used for various purposes.

  Thus, in another aspect thereof, an element for use in product packaging is provided herein.

  In some embodiments, the product is selected from food, cosmetics, pharmaceuticals, sealing products, electronic products, consumer products and pouch packaging.

  The XRF identifiable elements provided herein are subject to clear polymer product marking and certification that indicates whether the product has defects, whether the product has deviated from a predetermined continuous manufacturing process, or certain conditions after manufacturing. This can be used to detect and identify product deviations.

  Accordingly, in another aspect, a transparent element for use in marking an article is provided.

  In some embodiments, the marking includes authenticating or identifying the article.

  While not limited to only the following processes, the elements according to the present invention are described herein by means of extrusion techniques that involve depositing a relatively thin layer of the mixture as an independent element, or depositing a layer on the surface area of the product. Prepared from a mixture comprising a polymer of the type described and an XRF marker. The surface on which the element is deposited can be any surface that adheres to the element, such as glass, metal, ceramic, polymer or paper. The elements resulting from this procedure are flexible and have excellent physical properties. This element can be more easily oriented by stretching in one or preferably two mutually perpendicular directions.

Thus, in another aspect thereof, the present invention provides a process for manufacturing an element, the process comprising:
(I) extruding a mixture comprising a polymer and at least one XRF identifiable marker to obtain an extruded element;
(Ii) optionally applying uniaxial and / or biaxially oriented orientation to obtain an element.

  In some embodiments, uniaxial and / or biaxial stretching includes one or more stretch orientations selected from longitudinal stretching and transverse stretching.

  Markers utilized in accordance with the present invention can be dispersed in the polymers disclosed herein or in formulations to provide elements in accordance with the disclosed invention.

  In another aspect thereof, an amount of polymer and at least one XRF-identifiable marker sufficient to obtain a concentration of 50-300 ppm of XRF-identifiable marker in a transparent element comprising the polymer and at least one XRF-identifiable marker. A formulation comprising is provided.

  The concentration or amount of XRF identifiable marker in the formulation according to the invention is 50-300 ppm.

  In some embodiments, the formulation is 50-300 ppm, 50-290 ppm, 50-280 ppm, 50-270 ppm, 50-260 ppm, 50-250 ppm, 50-240 ppm, 50-230 ppm, 50-220 ppm, 50-210 ppm. Or at least one XRF-identifiable marker at a concentration of 50-200 ppm.

  In some embodiments, the formulation is 50-190 ppm, 50-180 ppm, 50-170 ppm, 50-160 ppm, 50-150 ppm, 60-200 ppm, 60-190 ppm, 60-180 ppm, 60-170 ppm, 60-160 ppm. , 60-150 ppm, 100-200 ppm, 100-170 ppm, 100-160 ppm at least one XRF-identifiable marker.

  In some embodiments, the formulation comprises 50-200 ppm of at least one XRF identifiable marker.

  The XRF identifiable markers utilized in the present invention can be dispersed in a formulation to provide a polymer element. Suitable materials as XRF identifiable markers in the formulations according to the invention are in the same form as the XRF markers described herein above, ie salts, inorganic or organic materials, metal ions, metal ligand forms or metals It may be in the form of a material containing atoms.

  In addition, the polymers suitable for the formulations according to the invention can be the same as those detailed hereinabove.

  In some embodiments, the polymer is a thermoplastic material.

  In some embodiments, the formulation comprises up to 50-300 ppm (0.005-0.03% w / w) of at least one XRF identifiable marker.

  The formulation may further include additives that provide desirable visual effects or physical properties to elements prepared from the formulation.

  In some embodiments, the formulation is for an antiblocking agent, an organic pigment, an inorganic pigment, a fluidity enhancing additive, a mechanical property enhancing additive, a non-tacky adhesive, an adhesion promoter, an adhesion inhibitor, a lubricant. Additives, antiwear additives, antistatic additives, marking additives, conductive additives, thermally conductive additives, magnetic improvement additives, insulating material additives, foaming agents, accelerators, catalysts, antioxidants, ultraviolet rays Further included are additives selected from stabilizers, flame retardants, pigments, stabilizers, wetting agents, empowers, diluents, wetting modifiers, dispersants, surfactants, diluents, thickening additives and fillers.

  Markers utilized in accordance with the present invention can be dispersed in the polymers disclosed herein or in formulations to provide elements in accordance with the disclosed invention (eg, dispersing markers in plastic solutions). By extruding, extruding, kneading, etc.). As such, the marker may be integrated into the polymer material or applied to the surface of an element made of polymer. To improve dispersion, a marker concentrate can first be prepared and then blended with the plastic by any standard processing method such as extrusion, molding, calendering, and the like.

  Typically, in an extrusion process, raw plastic is melted and formed into a continuous profile. The raw feedstock material is a solid plastic material, typically in the form of a resin, which is fed to the extruder barrel from a hopper attached to the top. Additives (liquid, powder or pellet form) such as colorants and UV inhibitors can be mixed into the resin before reaching the hopper or fed to the process via a separate feeder.

  Extrusion involves a helical feed screw that rotates inside the barrel (typically at a speed of up to 120 rpm). Screw or twin screw systems advance the material through the barrel where it is heated and compressed to a temperature above the melting point of the plastic. The molten plastic material is then extruded through the orifice.

  The XRF markers of the present invention can be added to the resin feed or secondary feeder for additives in resin, pellet, powder or liquid form. In addition, XRF markers can be prepared and included in pellets containing additional additives.

  In yet another aspect, there is provided a master batch mixture (ie, a concentrated mixture) comprising at least one XRF identifiable marker and a material selected from polymers, prepolymers, monomers, oligomers and additives; Contains 0.5% to 10% of this at least one XRF-identifiable marker. In some embodiments, the mixture is 0.5% to 8%, 0.5% to 7%, 0.5% to 6%, 0.5% to 5%, 1% to 5%, 1% % -6%, 1% -7%, 1% -8%, 2% -5%, 2% -6%, 2% -7%, 2% -8%, 2% -9%, 2%- 10%, 3% -7%, 3% -8%, or 3% -9% comprising at least one XRF identifiable marker.

  Such suitable materials are those combined with the XRF identifiable marker in an amount sufficient to produce a transparent element.

  In some embodiments, the additive is for an antiblocking agent, an organic pigment, an inorganic pigment, a fluidity improving additive, a mechanical property improving additive, a non-tacky adhesive, an adhesion promoter, an adhesion inhibitor, a lubricant. Additives, antiwear additives, antistatic additives, marking additives, conductive additives, thermally conductive additives, magnetic improvement additives, insulating material additives, foaming agents, accelerators, catalysts, antioxidants, ultraviolet rays Selected from stabilizers, flame retardants, pigments, stabilizers, wetting agents, empowers, diluents, wetting modifiers, dispersants, surfactants, diluents, thickening additives and fillers.

  In some embodiments, the masterbatch mixture is further added to a material selected from polymers, prepolymers, monomers, homopolymers and oligomers. Examples of such materials are known in the fields of extrusion, molding, spinning and kneading. In some embodiments, the material is a thermoplastic material or provides a thermoplastic material under sufficient conditions.

  The marker may be supplied to the manufacturing process with other additives, or may be inserted into the polymer resin prior to manufacturing.

  In some embodiments, the material is in a form selected from resins, pellets, powders and liquids.

  As discussed above, the XRF identifiable elements provided herein are transparent polymer product that provides an indication of whether the product has defects and whether the product has deviated from a predetermined continuous manufacturing process. It can be used for marking and authentication, or for detecting and identifying product deviations due to exposure to certain conditions after manufacture.

  An XRF identifiable mark formed on an article, e.g., a transparent thermoplastic product, is said to have a predetermined property that can be identified by XRF, thereby, e.g., deviating from a default specification of product manufacture or Enables judgment of product deterioration. The predetermined characteristic can be selected from the concentration of the XRF marker, the mark structure, size, shape, or chemical composition of the mark. If the mark is identified as being modified, the product can be considered degraded or out of its default manufacturing specifications.

  The resulting defective product may exhibit product thickness or wall thickness, bubbles and indentations, contamination with foreign objects, heterogeneity, and non-dispersed additive particle changes.

  Marks or patterns formed in / on an article may cause improper installation or operation of the extruder, undermixing of ingredients or addition of materials, overheating, surging temperature, oxygen, moisture, mechanical processing, repackaging, etc. Responds to at least one external stimulus.

  In some embodiments, the XRF-identifiable pattern has a predetermined shape, size and material configuration that changes upon exposure to an external stimulus (ie, which marker material is used at which concentration). Can be selected. In other words, the predetermined pattern is selected as an authentication mark that will be transferred to an unpredictable pattern that differs from its formed shape, size and configuration upon any deviation or degradation of the product. Have

Thus, in another aspect, a method is provided for authenticating a transparent article using an XRF identifiable mark, the method comprising:
(I) forming an XRF-identifiable pattern on at least one region of the transparent article, wherein the XRF-identifiable pattern has a predetermined property that is responsive to an external stimulus;
(Ii) irradiating the article with X-rays or gamma radiation at predetermined intervals;
(Iii) detecting an X-ray or gamma ray signal coming from the article in response to X-ray or gamma radiation applied to the article;
(Iv) applying spectral processing to the detected radiation signal to obtain data indicative of the presence, absence or any change of the predetermined characteristic.

  The concentration or amount of the XRF-identifiable marker of the present invention can be set according to a pre-selected encryption code that can be measured by XRF analysis at the authentication stage. In general, the marking pattern may include one or more markers having a preselected concentration in the range of 50-300 ppm, the preselected concentration being adapted or preset to encode a specific article identification. can do.

  The markers of the present invention can be added or applied to a transparent article so that their concentration on the surface of the article or in the bulk is set according to a preselected code. Thus, information can be encoded using markers. In particular, there is information regarding deviations from manufacturing.

  The sensitivity of detection and the resolution of marker concentration measurements can be enhanced by various methods for processing and enhancing the XRF signal received by the XRF reader, for example, improving the signal to noise ratio. For example, there are methods described in International Application PCT / IL2016 / 050340, which is incorporated herein by reference.

  Measurement of the concentration of the XRF marker at various locations and times of the continuous article can show changes and deviations, for example, as the thickness of the article changes. As the thickness of the article changes, the measurement radiation emitted by the marker changes. Other examples of changes or reductions in the measured concentration of XRF markers can also result from additive heterogeneity and / or poor dispersion, contamination, and foreign bodies accidentally introduced into the product during manufacture.

  Some other examples of measuring the concentration of XRF markers in an article include post-manufacturing use and can indicate the potential for product degradation due to exposure to UV light, heat, moisture, and the like.

  XRF measurements may be made at preselected intervals by the XRF analyzer at various times. Alternatively, XRF measurements can be performed “on-line” by an XRF analyzer that continuously measures articles and arrives from a marker over a preselected period that can vary from milliseconds to minutes. Average line counts (or counts per second-cps).

  The present invention provides a transparent article having at least one associated XRF identifiable pattern, such as the chemical composition of the pattern, the concentration of any one component present in the pattern, the pattern position, the pattern shape, etc. Based on one or more of them, it has a predetermined characteristic as a code for identifying the article.

  In some embodiments, the predetermined characteristic is responsive to an external stimulus by a transition from a predetermined (first) characteristic to a second characteristic, the transition being identifiable by XRF; Indicates exposure to this external stimulus.

  In yet another aspect, a method for marking a transparent element using an XRF-identifiable pattern is provided, the method forming a pattern of at least one XRF-identifiable marker on at least one region of the element. And the pattern having the first characteristic is responsive to an external stimulus by a transition from the first characteristic to the second characteristic, the transition being identifiable by XRF, indicating exposure to the external stimulus Yes.

  The XRF method (i) filters the wavelength spectrum profile of the detected portion of the X-ray signal coming from the article in response to X-rays or gamma radiation applied to the article, from the wavelength spectrum profile to the trend component and Suppressing the periodic component, thereby obtaining a filtered profile; and (ii) identifying one or more peaks in the filtered profile that satisfy a predetermined characteristic, thereby determining one or more peaks Making it possible to identify the signature of the material contained in the article using the wavelength.

  In some embodiments, the method includes irradiating the article with X-ray or gamma radiation, and detecting a portion of the X-ray signal coming from the article in response to radiation applied to the article. Applying spectral processing to the detected X-ray signal to obtain data indicative of its wavelength spectrum profile within a particular X-ray band.

  In some embodiments, the wavelength, and optionally also the size of one or more peaks, is used to provide material data that indicates the type and possibly further concentration of the material contained in the article, and thereby the article Determine any deviation or degradation received.

[Example 1]
BOPP film containing TiO ₂ marker (trade name Ti-Pure R104). The material was combined with the PP into a single concentrate with a PP homopolymer carrier of MFR 10-12. The marker content in the masterbatch was normalized to 1 wt% of the metal. A single concentrate was used to produce a 30 μm thick single layer cast film with a marker concentration of 100 ppm. This film showed no significant change in appearance compared to a reference film prepared in the same way without the addition of markers.

Claims (30)

A transparent element comprising a polymer and at least one XRF identifiable marker comprising:
The element comprises 50-300 ppm of the at least one XRF-identifiable marker;
A transparent element, wherein the element has at least one optical property substantially identical to at least one optical property of a polymer that does not include the at least one XRF-identifiable marker.   The element of claim 1, wherein the polymer is selected from polyolefins, polyamides, polystyrenes, polyesters, polycarbonates, polyethylene terephthalates, polyurethanes, polyamides, polyimides, polyacrylonitriles, polyvinyl alcohols and biaxially oriented polymers.   The element of claim 2, wherein the polyolefin is selected from polypropylene and polyethylene.   The element of claim 1, wherein the biaxially oriented polymer is biaxially oriented polypropylene.   The element of claim 1, wherein the at least one XRF-identifiable marker comprises at least one metal salt or a material comprising at least one metal atom.   6. The element of claim 5, wherein the at least one XRF identifiable marker comprises an atom selected from Co, Cu, Na, K, Zn, Ca, Mn and Ti.   6. The element of claim 5, wherein the at least one XRF identifiable marker is at least one metal salt.   The element according to claim 1, which is a film having a thickness of 10 to 100 μm.   9. Element according to claim 8, which is a film having a thickness of 20-60 [mu] m.   The element of claim 1, wherein the at least one optical property is selected from transparency, haze and gloss.   A laminate comprising at least one layer comprising the element of claim 1.   The laminate according to claim 11, further comprising at least one transparent layer.   The transparent element according to any one of claims 1 to 10, for use in marking an article.   14. An element for use according to claim 13, wherein the marking comprises authenticating or identifying an article.   11. Element according to any one of the preceding claims for use in product packaging.   14. An element for use according to claim 13, which is a film.   14. An element for use according to claim 13, wherein the product is selected from foods, cosmetics, pharmaceuticals.   Formulation comprising a polymer and at least one XRF-identifiable marker in an amount sufficient to obtain 50-300 ppm XRF-identifiable marker in a transparent element comprising said polymer and said at least one XRF-identifiable marker Wherein the formulation comprises up to 10% w / w of the at least one XRF-identifiable marker.   The formulation of claim 18, wherein the polymer is a thermoplastic material.   The XRF identifiable marker is potassium hydroxide, potassium iodide, potassium bromide, aluminum hydroxide calcium phosphite, calcium hydroxide hydrate, calcium butyrate, calcium chloride, calcium sulfoaluminate, 3,5-di- tert-butyl-4-hydroxybenzylphosphonic acid, monoethyl ester, calcium salt, titanium dioxide, titanium dioxide coated with a copolymer of n-octyltrichlorosilane and aminotris (methylenephosphonic acid) pentasodium salt, titanium nitride, Titanium dioxide nanoparticles reacted with octyltriethoxysilane, manganese pyrophosphate, manganese chloride, manganese hypophosphite, manganese oxide, manganese hydroxide, brass, bronze, copper, stainless steel, tin, and alloys of copper, tin and iron , Iron fluoride, iron phosphide, cobalt oxide, copper iodide, copper bromide, copper hydroxide phosphate, zinc sulfide, zinc hydroxide poly (zinc glycerolate) hexadecyltrimethylammonium bromide, sodium bromide, ammonium bromide 20. Formulation according to claim 19, selected from N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine-1,2-dibromoethane copolymer.   20. The formulation of claim 19, further comprising an additive selected from antioxidants, UV stabilizers, flame retardants, pigments, stabilizers and wetting agents. A masterbatch mixture comprising at least one XRF-identifiable marker and a material selected from polymers, prepolymers, monomers, oligomers and additives,
A masterbatch mixture, wherein the mixture comprises up to 10% w / w of the at least one XRF identifiable marker.   23. A masterbatch mixture according to claim 22, wherein the additive is selected from antioxidants, UV stabilizers, flame retardants, pigments, stabilizers and wetting agents.   23. A masterbatch mixture according to claim 22, wherein the mixture is further added to a material selected from polymers, prepolymers, monomers and oligomers.   Said at least one XRF identifiable marker is potassium hydroxide, potassium iodide, potassium bromide, aluminum hydroxide calcium phosphite, calcium hydroxide hydrate, calcium butyrate, calcium chloride, calcium sulfoaluminate, 3, 5 -Di-tert-butyl-4-hydroxybenzylphosphonic acid, monoethyl ester, calcium salt, titanium dioxide, titanium dioxide coated with a copolymer of n-octyltrichlorosilane and aminotris (methylenephosphonic acid) pentasodium salt, Titanium dioxide nanoparticles reacted with titanium nitride, octyltriethoxysilane, manganese pyrophosphate, manganese chloride, manganese hypophosphite, manganese oxide, manganese hydroxide, brass, bronze, copper, stainless steel, tin, and copper, tin And iron alloys, iron oxide, iron phosphide, cobalt oxide, copper iodide, copper bromide, copper hydroxide phosphate, zinc sulfide, zinc hydroxide poly (zinc glycerolate) hexadecyltrimethylammonium bromide, bromide 23. The method of claim 22 selected from sodium, ammonium bromide, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine-1,2-dibromoethane copolymer. Masterbatch mixture.   23. The masterbatch mixture of claim 22, wherein the material is a thermoplastic material or provides a thermoplastic material under sufficient conditions.   23. A masterbatch mixture according to claim 22, wherein the material is in a form selected from resin, pellets, powder or liquid. A method for authenticating a transparent article using an XRF identifiable mark, the method comprising:
(I) forming an XRF-identifiable pattern on at least one region of the transparent article (wherein the XRF-identifiable pattern has a predetermined characteristic responsive to an external stimulus);
(Ii) irradiating the article with X-rays or gamma radiation at predetermined intervals;
(Iii) detecting an X-ray or gamma ray signal coming from the article in response to the X-ray or gamma radiation applied to the article;
(Iv) applying spectral processing to the detected radiation signal to obtain data indicating the presence, absence or any change of the predetermined characteristic;
Including a method.   30. The method of claim 28, wherein the predetermined identifiable characteristic comprises a concentration or encryption code of the XRF identifiable pattern.   A method for marking a transparent element using an XRF-identifiable pattern, the method comprising forming a pattern of at least one XRF-identifiable marker on at least one region of the element, the pattern Has a first characteristic that is responsive to an external stimulus by a transition from a first characteristic to a second characteristic, the metastasis being identifiable by XRF, indicating exposure to the external stimulus, Method.